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By E. T. Turkdogan, P. Grieveson

It is shown experimentally that, by making use of the coupled S-O reaction in ionic melts, it is possible to transfer slclJur or oxygen from a lozv to a high chemical potential through an ionic nzenzbrane. This uphill transfer of sulfur is accompanied by a counter downhill transfer of oxygen and vice versa. The Materials balance shows that the amoulits of sul -fur and oxygen lost or gained by one system are the same as those gained or lost by the other systenz — the two systejns being separated by an iofzic membmne. The systems used in these experi?nents were solid Mn-MnS-Mno and liquid Fe-S-0. Sufficient results were obtained Lo study the kinetics of the transfer and the indications are that the counter diffusion of sulfide and oxide iojzs in the membrane is the rate controlling process. WHEN an ionic oxide-melt reacts with an atmosphere containing sulfur and oxygen-bear ing gases the following reaction occurs: 1/2 S2 (gas) +O2- (melt) = S2- (melt) + 1/2 0, (gas) [1] Under the restrictions that i) electric conductance in the melt is purely ionic and ii) each constituent element in the melt does not change valence, the solution of an atom of sulfur in the melt will result in the evolution of an atom of oxygen, so that the electric neutrality is maintained. For a given temperature and melt composition, the equilibrium concentration of sulfur in the melt is determined by the ratio, po2 /ps2 , in the gas phase and not by the individual partial pressures of oxygen and sulfur. This has been demonstrated by a number of investigators, for example by Richardson and withers', Fincham and Richardson,la by St Pierre and Chipman,' and by Turkdogan and Darken.3 In his Howe Memorial Lecture for 1961, Darken discussed the possibility of uphill pumping of sulfur through an ionic membrane at the expense of oxygen. TO test the validity of this concept associated with coupled reactions, experiments were carried out in the following manner. A presintered mixture of Mn-MnS-MnO and prefused mixture of Fe-S-0, contained in platinum and iridium crucibles, respectively, and separated by a thin layer of soda-glass (to act as an ionic membrane), were placed side by side in an evacuated silica capsule and sealed. This was then kept at 1400°K for a required time to allow Reaction [11 to occur via the ionic membrane. When partial equilibrium is reached, the ratios Po2 /pS2, for systems on either side of the membrane, are equal and the flux of sulfur and oxygen through the membrane becomes zero, although the individual partial pressures po2 andp,, in these two systems may differ considerably.

Jan 1, 1962

By F. G. Tahmoush, N. J. Grant, E. P. Abrahamson

The effect of grain size on the brittle -ductile transition temperature of pure iron and three dilute Fe-W alloys has been investigated by slow bend tests. The brittle-ductile transition temperature for pure iron increased with increasing grain sizes from 8000 to 500 grains per sq mm where the transition temperature then decreased with further increase in grain size. The dilute additions of tungsten lowered the transition temperature for fine grain sizes, suppressed a reversal of the curve in the coarse grained portion, and raised the transition temperature for this region. The frequency of twin occurrence increased with increasing grain size and decreasing temperature. The object of the present investigation was to re-examine the effect of grain size on the brittle -ductile transition of pure iron and several dilute Fe-W alloys. Current literature normally presents a simple relationship between grain size and the brittle-ductile transition temperature, namely, that the transition temperature increases with increasing grain size. Heslop and etch' have studied the transition temperature of mild steel by V-notch Charpy impact tests for the grain size range between 200 and 6000 grains per sq mm. The result was a linear plot of In 1-1/2 vs brittle-ductile transition temperature, where 1 is the grain diameter. Recent experiments by sipos2 revealed the possibility of a reversal in the slope of the grain size vs transition temperature plot for pure iron; however, his investigation was limited in scope, and the data obtained were insufficient to permit a definitive curve. The present investigation was undertaken in an effort to confirm or extend the grain size effect observed in iron by Sipos. PROCEDURE All alloys were vacuum induction melted, using 99.95 pct Fe containing 0.03 pct 0 and 0.004 pct C. Four ingots were made, ranging from pure iron to iron with 0.035 pct W. The chemical composition of each alloy, after processing, is given in Table I. The four alloys were prepared as 45 lb heats and cast into 4 in. diam by 16 in. molds. They were then extruded into 3/4 in. rods at 1800oF. Specimens for chemical analysis, taken from various positions along the rods, revealed no variation in tungsten content along the length. The extruded rods were reduced to 0.156 in. diam stock by a series of cold swaging operations involving intermediate vacuum annealing treatments. This procedure yielded a final cold reduction in area ranging from 10 to 90 pct. The swaged rods were chemically cleaned, cold pressed to a cross section of 0.10 by 0.18 by 1.0 in. long (2.54 by 4.73 by 25 mm). The specimens were wrapped in iron foil and vacuum sealed (10-4 mm Hg) in quartz. Various heat treatments at temperatures from 700" to 1300oC were utilized to produce grain sizes from 8000 to 1 grain per sq mm. Grain sizes were determined by measuring the average area of grains in a polished section. In specimens with grain size greater than 20 grains per sq mm, the total number of grains in the cross section was counted and then divided by the area to yield grains per sq mm. Grain size was measured both for longitudinal and transverse cross sections. The average of the two measurements was plotted vs transition temperature. An Instron Table Model testing machine was used to determine the transition temperature of specimens tested in three point horizontal bending. The specimen was supported by two 1/4 in. dowels one in. apart. Bending was accomplished with a push rod, the end of which had an 1/8 in. radius. The head speed was 50 in. per min. Temperatures were established through the use

Jan 1, 1963

By M. Prats

This paper presents a method for obtaining the correct values of the breakthrough sweep efficiency of the staggered line drive, taking into account the proper shape of the breakthrough streamline. Results obtained were different from those previously published, which were obtained by using an inexact shape of the breakrhrough streamline. INTRODUCTION In Section 9.31 of Muskat's' The Flow of Hotnogeticous Fluids Through Porous Media, it is stated that in a staggered line drive flood "the streamline of highest average velocity [is] the line of centers between input and output wells" (see Fig. I). Muskat used this concept to determine the relationship between the breakthrough sweep efficiency and the geometry of the staggered line drive pattern. Although it is clear from symmetry considerations that the breakthrough streamline passes through the midpoint between input and output wells, it is equally clear, as shown in Fig. 239 of Ref. 1, that the breakthrough streamline is not represented very well by the straight line joining the input and output wells. Therefore, it is desirable to determine the proper relationship between the breakthrough sweep efficiency and the pattern geometry by using the proper shape of the breakthrough streamline. METHOD OF SOLUTION It was found that the effect of the geometry of the staggered line drive on the breakthrough sweep efficiency can be investigated easily by making use of the method developed in Ref. 2. With this method, it can be shown that the general complex potential for the staggered line drive, which can be considered as a rectangular five-spot, is given in the coordinate system of Fig. 1, by O(z) = In cn(z\m) = +(x,y) + i $(x, y) . (1) where z = x + iy, +(x, y) is the potential distribution and $(x, y) is the stream function. The function cn (zm) is a Jacobian elliptic function of parameter m and has simple zeros at z,. = (2n + 1) K + 21iK and simple poles at z, = 2nK + (21 + 1)iK. Thus, the complex potential behaves like a(z) = ln(z - zr.) in the neighborhood of the production wells and behaves like a(z) = - ln(z - Z,) in the neighborhood of the injection wells. Since (z - z1.v) = rll.ei, we note that the potential + has the proper logarithmic behavior near the two wells, while the stream function $ varies with the angle, decreasing clockwise around the production well and increasing clockwise around the injection well. The functions K(m) and K'(tn), related by K(m) = K'(m,), where m + m, = 1, are known as the complete elliptic integrals of the first kind. By use of other properties of the Jacobian elliptic functions, the general stream function distribution for the staggered line drive can be obtained from Eq. 1: From the Jacobian elliptic function values, sn(0lm) = 0 dn(O(m) = cn(0jm) = 1, and f[K'(m)Iml = 03, it follows that the stream function given by Eq. 2 satisfies the proper symmetry conditions near a production well P located at [K(m), 01 and an injection well I located at [0, K' (m)]. That is, the line IOP in Fig. 1 is a streamline with value G (0. 0) = -0. and the straight lines connecting I and P to the point [K(m), K' (m)] is a streamline of value $[K(m), K' (m)] = -7/2. Similar symmetry conditions are obtained near other wells. It should be nuled that for m = m1, = 0.5, Eq. 2 reduces to the stream function distribution of the regular five-spot given in Ref. 7. SHAPE OF THE BREAKTHROUGH STREAMLINE It is apparent, from symmetry considerations, that the breakthrough streamline ($,) passes through the point [K(m)/2, K' (m)/2]. Its value there is so that the shape of the breakthrough streamline $,, is given by

Jan 1, 1957

By St. John, JOHN Ancel

AT THE New York meeting of the Institute of Metals Division in February, 1927, Jeffries and Tarasov presented a paper on Tungsten and Thoria,1 in which the experimental facts were interpreted in accordance with the prevailing point of view that the thorium is present as the oxide, thoria. In discussing that paper the writer of this article stated that his own investigations, which had been unavailable to Messrs. Jeffries and Tarasov, showed that the so-called "thoriated" tungsten filament failed to disclose any sign of the oxide when subjected to X-ray diffraction analysis, but did give plenty of evidence of the presence of metallic thorium and, in certain cases, of a material believed to bean alloy of tungsten in thorium. Since these results were completely at variance with the results reported in the paper under discussion and with other papers which had preceded it from time to time in the past, it was felt that further discussion should be withheld until the new evidence could be presented adequately. Arrangements were therefore made to present that evidence at this meeting. MATERIAL EXAMINED The material examined was high-emission filament such as is used in radio tubes, supposed to contain about 0.75 per cent. thoria. The actual analysis was not stated.

Jan 1, 1927

By Paul A. Farrar, Louis P. Stone, Harold Margolin

The Ti-Mo-0 system was investigated in the region 0 to 45 wt pet Mo and 0 to 10 wt pet 0, from 600° to 1400°C. Solidus data are also presented. Isothermal sections at 700°, 900°, 1100°, and 1300°C, and vertical sections at 1 and 28 wt pet Mo, and 1 and 10 wt pet 0 are included. STUDY of the Ti-Mo-0 system has been carried out as part of a general study of titanium phase diagrams. The binary Ti-Mo system has been investigated in whole or in part by several investigators.1-8 It was found that molybdenum and ß-tita-nium form a complete series of solid solutions and that the ß/a + ß transus is depressed to below 600°C at approximately 30 pet Mo.* The Ti-O system has been investigated partially or fully in the range 0 to 30 pet 0 by several investigators." Extensive solubility of oxygen occurs in the field. While a is

Jan 1, 1957

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.' In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.' Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.',' It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.' In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

By Gerald G. Griswold, James O. Greenslade, Cherie Tilley, Richard Reseigh

INTRODUCTION The Harrison Western Corporation, a leading Denver based mine contracting and engineering concern, is presently engaged in sinking two 1,006 m (3,300 ft) shafts for the Phillips Uranium Corporation at their Nose Rock Project, approximately 13 miles northeast of the small community of Crownpoint in McKinley County, New Mexico. The Nose Rock Project is the first attempt by the Phillips Uranium Corporation to tap the deep uranium reserves in what has become known as the Grants Mineral Belt. (See Figure 1) Project Description Phillips Uranium Corporation's plan for the large 2700 metric ton per day (2950 tons/day) mining facility calls for a series of deep access and ventilation shafts ranging from 4.27 m (14 ft) to 5.49 m (18 ft) in diameter to approximate depths of 1,006 m (3,300 ft). The initial pair of shafts consists of one production shaft and one ventilation shaft separated by a distance of 91 m (300 ft). The interbedded layers of sedimentary sandstones and shales to be penetrated by the shafts contain several major water producing aquifers, the deepest being the mineralized zone called the Westwater Canyon Member of the Morrison Formation. A series of temporary and permanent water pumping stations is planned. Generally, the temporary stations are located above major aquifers to facilitate water removal while sinking through the aquifer and the permanent stations constitute what, in the final mode, will be the mine dewatering system. In addition, Phillips Uranium Corporation has In- stalled and is maintaining a system of depressurization wells that temporarily pump the major aquifers and considerably reduce the water inflows during shaft construction. The major aquifers are also chemically grouted prior to sinking. Site work for the project was initiated in the fall of 1976. Full scale shaft sinking commenced in November of 1977 on the 4.88 m (16 ft) diameter ventilation shaft and on the 5.49 m (18 ft) production shaft by another contractor. Harrison Western Corporation began work on the project on November 4, 1979 wlth the production shaft at a depth of 633 m (2,076 ft) and the ventilation shaft at a depth of 474 m (1,554 ft). This paper will address only the portion of shaft sinking completed by Harrison Western. Geology and Hydrology The Nose Rock Project is located on the Chaco Slope in the southern extreme of the San Juan Basin in northwest New Mexico. The southern San Juan Basin is generally bound by the Defiance Uplift to the west, the Zuni Uplift to the south and the Nacimiento Uplift to the east. The Grants Mineral Belt occupies most of the southern portion of the San Juan Basin and this project is located on the northern extreme of the Grants Mineral Belt. The San Juan Basin is comprised of sedimentary rock of continental, marginal-marine and marine origin, that dip northward from the Zuni Uplift and Chaco Slope into the interior of the San Juan Basin. (See Figure 2) Major Formations The major geologic formations to be penetrated range from mudstone and shales to siltstones and sandstones. The sandstones are highly productive aquifers which, under static conditions, would flow artesian. Water temperatures in the aquifers are high and therefore are a force to be dealt with. Temperatures range from 18ºC (65OF) in the upper aquifers to 48ºC (118º'F) in the lower. The mudstones are generally bentonitlc. (See Figure 2) GALLUP SANDSTONE: The Gallup Sandstone is the first major regressive wedge in the San Juan Basin of the Cretaceous era and at this project is about 35 m (115 ft) thick. It is medium grained and prior to depressurization carried a hydrostatic water pressure of over 72.5 kg per cm2 (1,031 psi) which 1s artesian. Compressive strength ranges from 334.7 kg per cm2 (4,760 psi) to 421.8 kg per cm2 (6,000 psi). Water temperature is approximately 30°C (86°F).

Jan 1, 1982

By FRED T. WILLIANS

INTRODUCTION. THE Park City mining-district is distinctively a camp of few properties, 5,000 acres, or one-third of the entire district, being under the management of but three companies. As a rule, the ore-bodies lie deep, with no outcrop, except where erosion has formed the deeper canyons and gulches. Ontario canyon exposed the famous Ontario ledge, and Woodside gulch showed the first ore of the Silver King Coalition mine. The Quincy ore-bodies were first brought to light in upper Empire canyon, and Thaynes canyon was instrumental in aiding the prospector during the early days of the camp. There are 22 shafts which have reached a depth of at least 500 ft., ten a depth of 1,000 ft., five a depth of 1,300 ft., and two a depth of 2,000 ft. The amount of lateral development has been proportionally extensive, including six long tunnels, four of which are in 3 miles, with a fifth now being driven. The Ontario lower drain-tunnel is now more than 4 miles long. The formations are sedimentary, dipping about 30° NW. and N., and traversed by many fissures, dikes, and faults. The principal ore-bodies are found associated either with the contact of the basal Ontario quartzite and the overlying limes, or on a quartzite stratum within the limes, or in the fissures, or along some of the porphyry dikes. The district covers the intersection of the Uintah and Wasatch ranges, which explains the existence of large folds and faults, and fissures of great length, width, and depth. In a general way, the geology of the district consists of a basal quartzite dome, which has been exposed by erosion at the Ontario property. The Ontario fissure lies entirely within this formation. Flanking this dome on the west, north, and east lie

Jun 1, 1911

By F. X. Tartaron

This paper deals with basic physical phenomena, which when combined and interpreted, lead to the same mathematical equations that describe comminution phenomena. Thus, a physical model is described that corresponds to the mathematical model presented in the writer's previous papers. '12 In the mathematical model, the energy consumed in breakage is related to the volume or weight of material broken and the size of particles broken. The equation E=2.303 Ck-a log x1/x2 was derived by multiplying the volume or weight of each size in an ideal Gates-Gaudin-Schumann size distribution by an energy factor. The product of these two factors gives the energy distribution among the different sizes in a single size distribution. The energy of breakage of a specific constant weight of one size distribution to another size distribution is given by the equation E = constant/kn-1. In this case, where the volume or weight is constant, the energy is proportional to the size factor 1/kn-1. In what follows, a physical theory will be presented showing that the energy consumed in comminution is proportional to the volume or weight of the material broken and to the reciprocal of the size of this material raised to a constant exponent. THE VOLUME FACTOR The atomic theory of matter reveals that in solids, atoms or ions are arranged so as to be in equilibrium at specific distances from one another. Although the atoms or ions are oscillating, there is a definite determinable mean distance between them and this distance is a balance between repulsive and attractive electrical forces. It therefore requires force to separate the atoms or ions and when an outside force is applied, it first produces strain in increasing the distance between the atoms or ions. This strain increases to the breakage limit on application of sufficient force. In brittle materials, there is negligible plasticity and when an elastic limit is exceeded, breakage takes place. The work done is the force applied per unit area times the cross sectional area of the ideal particle multiplied by the maximum strain per unit length at right angles to the area times the length of the particle. Thus the work done is proportional to the area times the length, which is equivalent to the volume of the ideal particle. If more than one feed particle is considered broken, each particle must be subjected to sufficient strain so that the breakage limit of its contained atoms or ions is reached in order for the particle to be broken. Thus, the energy of breakage is proportional to the total volume of the particles broken. If the particles are of different sizes, the size factor must be included to get a correct determination of energy of breakage. In the preceding, it has been assumed that there is a constant binding force between the atoms throughout the volume being strained. This, of course, is not true. It is known that there are many irregularities in the structure of matter and the binding force differs markedly in different portions. But the differences are only discernible by examining extremely small subdivisions of matter. In one order of magnitude of volume, cracks can be discerned separately from non-cracked neighboring material. In a smaller subdivision of volume, lattice dislocations can be isolated. When these situations are brought into focus, mechanisms of their behavior can be learned, leading to a fuller understanding of phenomena that occur in larger scale subdivisions of matter. Very often, however, the mechanisms that operate in small scale subdivisions have negligible effect in those of large scale, and there still is a place for deriving a mechanism for large scale conditions. The quantum theory is extremely valuable for use with photons and electrons, but is of negligible use with ordinary atoms and molecules. This paper deals with relatively large scale subdivisions of volume present in comminution phenomena. Hence, the effects of cracks, lattice dislocations, misplaced atoms, etc., are smoothed out in an average, constant for each relatively large subdivision of volume. This attitude is supported by experience. If two 10 cc samples of the same ore were ground identically, the same product would be obtained. However, if two samples, each a cubic micron, were conceived to be broken, then one sample might contain a crack and the other not, hence a different product would be obtained. Experience shows that ordinary samples used in comminution, behave as though no irregularity existed

Jan 1, 1964

By Mark J. Klein

The creep of 043 was studied over the temperature range 1650" to 3200°F and over the stress range 3000 to 44,000 psi. The steady-state creep rate over this range of stress and temperature can be expressed by the equation where A is a constant, is the stress, and is -0.8 x 103 psi-'. Over a narrow range of stress variations c0 a and for this proportionality n varies from 3 to 30 in accordance with the relation n = aB. Above about 2400° F, H, the apparent activation energy for creep, is 110,000 cal per mole, a value about equal to that estimated for self-diffusion in this alloy. Below 2400°F, H increases with decreasing temperature reaching a value of -125,000 cal per mole at 1700° F. In this temperature region, H appears to be a function of the interstitial concentration of the alloy. MOST of the detailed creep studies of dispersion strengthened metals have been concerned with metals having fcc structures. However, there are a number of important refractory alloys with bcc structures that derive part of their high temperature strength from an interstitial phase and whose creep behavior has not been well defined. This paper describes the creep behavior of the bcc alloy, D43, over the temperature range 1650" to 3200°F (0.4 to 0.7 Thm) and over the stress range 3000 to 44,000 psi. In addition to colum-bium, this alloy contains 10 pct W. 1 pct Zr, and sufficient carbon (-0.1 pct) to form a carbide dispersion throughout the matrix of the alloy. The effects of variations in temperature and stress on the steady-state creep rate of this alloy are presented in this paper. EXPERIMENTAL PROCEDURES Creep tests were made in a vacuum of 106 torr under constant tensile stress conditions using a Full-man-type lever arm.' Creep specimens were machined from 0.020-in. D43 sheet (grain size -5 x l0-4 in.) processed in a duplex condition (solution annealed -2900°F, 40 pct reduction in area, aged 2600°F). The specimens were tested in this condition without further heat treatment. Specimen extensions over 1-in. gage lengths were continuously recorded using a high temperature strain gage extensometer. Differential temperature and stress measurements were used to determine temperature and stress dependencies of the creep rate. Activation energies were calculated from the changes in strain rate induced by abrupt shifts in the temperature during constant stress creep tests. The 100°F temperature shifts used in most of the activation energy determinations required 15 to 90 sec depending upon the temperature at which the shift was made. The dependence of strain rate on stress was determined by measuring the change in strain rate for incremental stress reductions during constant temperature tests. It has been shown that columbium-base alloys such as D43 are susceptible to contamination by gaseous interstitial elements during vacuum heat treatments.' In this regard, it is unlikely that these alloys can be heat treated without some loss or gain of interstitial elements despite the precautions taken to control the heat treating environment. However, several factors suggest that changes in interstitial concentrations of the specimens during testing did not affect the results presented in this paper. First, the dependence of the creep rate on the stress or temperature determined during the course of a single creep test showed no variations with the duration of the test. A variation would be expected if a loss or gain in interstitial concentration during the course of the test affected results. In addition, precautions taken during this investigation to minimize interstitial contamination by wrapping the gage lengths of the specimens with various foils2 (Mo, Ta, W) did not produce a detectable change in the stress and temperature dependencies relative to the unwrapped specimens. The averages of duplicate analyses for carbon and oxygen in several specimens determined before and after creep testing are listed in Table I. The combined nitrogen and hydrogen concentrations which were ordinarily less than 50 ppm did not change in a detectable way with creep testing. The analyses show that only minor changes in carbon concentration occurred during creep testing except for specimen 4. This specimen which was tested at 3100°F lost a significant amount of its carbon concentration to the vacuum environment. Specimen 1 gained 100 ppm of O, while specimens 2, 3, and 4, which were tested at progressively higher temperatures, lost increasing portions of their initial oxygen concentrations during testing. RESULTS AND DISCUSSION The Temperature Dependence of the Creep Rate. The apparent activation energy for creep, H, was de-rived from creep curves similar to that shown in Fig. 1. Steady-state creep was rapidly attained at the beginning of the test and with each change in temperature. This behavior suggests that the alloy rapidly attains a stable structure with each shift in temperature or that the structure is constant throughout the test. Since the dispersion will tend to stabilize the structure, the latter is probably the case. The activation energy was found to be independent of the direction of the temperature shift and the magnitude of the shift (50" or 100°F). Although H was approximately independent of the strain, there was a tendency for it

Jan 1, 1970

By T. H. Janes

NATURAL abrasives of some type are found in all countries of the world. In order of their hardness the principal natural abrasives are diamond, corundum, emery, and garnet, which are termed high grade, and the various forms of silica, including pumice, pumicite, ground feldspar, china clay and, most important, sandstone. The properties qualifying materials for use as abrasives are hardness, toughness, grain shape and size, character of fracture, and purity or uniformity. For manufacture of bonded grain abrasives such as grinding wheels, the stability of the abrasive and its bonding characteristics are also important. No single property is paramount for all uses. Extreme hardness and toughness are needed for some applications, as in diamonds for drill bits, while for other purposes the capacity of the abrasive to break down slowly under use and to develop fresh cutting edges is of greatest importance, as with garnet for sandpaper. In dentifrices, soaps, and metal polishes, of course, hardness and toughness are objectionable. First among the natural abrasives, industrial diamonds are essentially of three types: l—bort, which includes off-color, flawed, or broken fragments unsuitable for gems; 2—carbonado, or black diamond, a very hard and extremely tough aggregate of very small diamond crystals; and 3—ballas, a very hard, tough globular mass of diamond crystals radiating from a common center. Bort comes from all diamond-producing centers, carbonados only from Brazil, and ballas chiefly from Brazil, although a few of this last group come from South Africa. By far the largest producer of industrial diamonds is the Belgian Congo; the Gold Coast, Angola, the Union of South Africa, and Sierra Leone supply most of the remainder. There is no production in Canada, which imports $6 to $9 million worth of industrial diamonds annually. Industrial diamonds find innumerable uses in modern industry. They are used for diamond drill bits for the mining industry; in diamond dies for wire drawing; in diamond-tipped tools for truing abrasive wheels and for turning and boring hard rubber, fibers, and plastics; and in diamond-toothed saws for sawing stone, glass, and metals. High-speed tool steels, cemented carbides, and other hard, dense alloys can be cut, sharpened, or shaped efficiently only with diamond-tipped tools and diamond grinding wheels. .. Second only to the diamond in hardness is corundum, an impure form of the ruby and sapphire gems consisting of alumina and oxygen (Al²O³) with impurities such as silica and ferric oxide. Corundum generally crystallizes from magmas rich in alumina and deficient in silica, as in the nepheline syenites of eastern Ontario. Grain corundum is used in the manufacture of grinding wheels; very coarse grain is used in snagging wheels. Both types of wheels are employed in the metal trades, where the hardness of corundum, coupled with its characteristic fracturing into sharp cutting edges, makes it an ideal cutting tool. The finest corundum (flour grades) is used for fine grinding of glass and high-precision lenses. From 1900 to 1921 Canada was the world's leading producer of corundum. Following this period the deposits located in northern Transvaal of the Union of South Africa supplied more and more of the world's requirements, and since 1940 South Africa has provided almost the entire output, which has ranged between 2500 to 7000 tons a year during the last decade. Minor amounts have also been produced in Mozambique, India, and Nyassaland. Opportunities for Mining Corundum Corundum deposits in southeastern Ontario are of three types, which may be described as follows: 1—Scattered, irregularly-shaped deposits of coarse-grained corundum which could be mined by means of small pits. About 10 groups of such deposits are known. Although the tonnage of individual deposits of this type is not great, it has been estimated that several years' ore supply is available for a small tonnage operation. Deposits average about 9 pct corundum. 2—Large irregular deposits of coarse-grained corundum which would require mining by adit with possibly a scavenger operation on the remains of former surface deposits. The Craigmont deposit of this type produced about 20,000 tons of corundum concentrate during operations between 1900 and 1913. Most of the readily available surface ore was removed by operators during that time. Reserves of ore above road level have been estimated to average 7 pct corundum, but none of the so-called reserves have been blocked out, or even indicated, by diamond drilling. From 1944 to 1946, 2025 tons of

Jan 1, 1955

By J. C. Holm

ALTHOUGH the main constituents of Portland cement are the oxides of calcium, silicon, aluminum, and iron, characteristics of the cement are seriously affected by such contaminants in the raw materials as magnesium, phosphorus, sodium, potassium, sulfur, and others of lesser importance. Sources of cement raw materials comprise a long list of minerals occurring in nature in various degrees of purity. The calcareous raw materials are generally limestone of purity varying from calcite to cement rock (a low-grade limestone of natural, almost correct chemical composition), chalk, marl, seashells, coral, and coral sand. The argillaceous raw materials supplying silicon, aluminum, and iron are mainly various forms of clay and shale, to which may be added silicious sand, iron ore, bauxite, or kaolin for minor adjustment of the chemical composition. The quality of Portland cement in this country, as in most parts of the world, is controlled by rigid specifications limiting both its chemical and physical characteristics, and cement manufacturers must comply with these specifications to market their products. Brandon Raw Materials: An unusual deposit of marl, limestone, and clay occurs 12 miles east of Jackson, Miss., near the village of Brandon. The deposit is of sedimentary origin and of relatively young geological age. Layers of marl vary from putty-like consistency to such hardness that it can be cut with a knife. Interspersed between the layers of marl are bands of limestone varying from very soft to hard. the compressive strength of the hardest layers exceeding 15,000 lb per sq in. The layers of marl range in thickness from a few inches to about 25 ft. The limestone bands seldom exceed 2 to 3 ft but often occur in thinner veins in the quarry face. Above the top layer of the deposit, which may be marl or limestone, a layer of clay ranges in thickness from a few inches to more than 20 ft. Part of this clay is harvested with the raw material to supply part of the argillaceous components, but most of it is stripped as overburden and wasted. A highly silicious clay of extreme fineness, harvested from the bottom of the quarry below the marl and limestone bands, is to correct the silica content. Fig. 1 shows typical examples of the interrelation of the various materials, based on drill logs obtained during exploration of the deposit. The marls vary in moisture content in the bank from 15 to 30 pct and contain up to 70 pct -200 mesh particles and up to 40 pct —10 p particles. A large percentage of the fine fraction is within the colloidal range, making the marl extremely sticky. The limestone beds range in hardness from that of the hardest marl to a medium hard limestone and in moisture content from 2 pct to approximately 14 pct. The line of demarcation is often difficult to draw and the moisture content is possibly the best means of classification. The ratio of soft to hard material is not constant throughout the deposit, but the average is approximately 70 pct soft to 30 pct hard material. Through the years this deposit had been repeatedly explored by cement companies and rejected as unsuitable for cement manufacture, mainly because of physical characteristics. In 1950, after careful exploration of the deposit and comprehensive laboratory and pilot plant tests of the raw materials, officials of Marquette Cement Mfg. Co. of Chicago were convinced that a practical and economical method of processing the raw materials had been devised and authorized construction of a new plant that began production in December 1951. Marl and limestone, common raw materials for Portland cement, usually occur in such a manner that they can be worked separately. Their harvesting and processing normally have presented no difficult problems, as standard equipment and methods are available for handling either sticky or hard materials. No other cement plant utilizes a deposit of the nature of that at Brandon, however, and for this reason no prior art was available for design. When properly blended, the raw materials produced an excellent cement without additives. Basic problems to be solved in designing the cement plant were:

Jan 1, 1957

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By W. N. Poundstone

The mining and ventilating system used in development work in the Pittsburgh Seam in northern West Virginia is discussed. The seam conditions and the nature of the accompanying methane gas are described. The type of equipment and the mining cycle will be discussed, showing how they are well suited for very gaseous development work. Face ventilation in development work is possibly the fastest growing problem of the industry. The coal mines of the future will be faced with the prospect of mining from under increasing depths of cover. Consequently, larger and larger amounts of methane gas probably will be found. The Pittsburgh Seam, in northern West Virginia, is an example of an area already faced with this problem. At the present time, most of the development work being done in this seam lies beneath 500 to 1200 ft of cover. The Pittsburgh Seam in this area has always been very gassy—even near the outcrop—and the recent development work has been accompanied with extremely large volumes of gas. In many cases, a single development section has liberated in excess of 1,000,000 cfm in 24 hr. This problem of heavy gas liberation was the chief concern, several years ago, when continuous mining equipment was first considered at Christopher Coal Co. All of us were apprehensive about the liberation that would accompany rapid extraction in a single working place. However, the experience during the past few years has shown that this ability to mine only one place at a time, is actually the key to working this type of coal. With all of the mining or advancement concentrated in one place, the ventilation can also be concentrated. By this it is meant that continuous mining permits the active working place to be ventilated with a maximum amount of fresh air, taken directly from the intake source without first passing another working place. Continuous mining (and a good ventilating system) also permits a much greater concentration of attention or vigilance to the actual working place. There are two things that are very important to the mining of coal having high rates of liberation. First, adequate volumes of air are necessary. Second, and perhaps more important, a mining and ventilating system must be used that will provide an uninterrupted flow of air to every portion of the working section. Liberations of this magnitude take only a few seconds of interruption for a dangerous accumulation of gas to occur. With adequate volumes of air available, the ability to concentrate ventilation more than offsets the concentration of gas emission that is inherent with continuous mining. The mining system used with continuous mining equipment at Humphrey Mine is similar to the system used at many mines in the area for development work. This system is designed to favor ventilation, realizing that other efficiencies are meaningless if the equipment must stop because of ventilation difficulties. This plan is especially well suited to minimizing ventilation interruptions. Basically, the overall plan of mining is to develop headings into virgin coal and encircle or block out large areas. These blocks are generally at least 2000 ft sq. The purpose of this blocking out is to bleed gas from the area before pillaring. Experience has shown this method to be quite effective, even in the most gassy areas. The gas in this field seems to migrate or flow readily from the solid coal into the outside return headings of the development work. The numerous clay veins and slips that are found in the area are extremely good avenues for gas flow. A block of coal, surrounded with development headings, usually bleeds off readily; and since it is cut off from the virgin coal, it is not subject to gas migration, through the seam, from this source. However, the outside return of the encircling development work, adjacent to the virgin coal, may liberate gas for years. This liberation from the outside ribs in the virgin coal is the reason split ventilation is used in development work. If split ventilation were not used, there would, in many cases, be a serious build-up of gas in the intake before it could reach the working face. Fig. 1 shows a typical development section having seven headings. The two outside places on each side are returns, and the three center headings serve as intakes. This section is equipped with a ripper-type continuous mining machine. An off-track loading machine is used to load from a surge pile on the

Jan 1, 1961

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By D. V. Edmonds, C. J. Beevers

Tensile tests were carried out on a! titanium containing 850, 1250, and 2700 ppm 0, and up to -500 ppm H. The tests were performed at -196", -78", 20°, 150°, and 300°C at a strain rate of -1.0 x 10??3 sec-1. Increasing oxygen content, increasing grain size, and decreasing test temperature resulted in enhanced embrittlement of the a titanium by the hydrogen additions. Metallographic observations showed that this can be correlated with the influence of these parameters on the introduction of cracks into the a! titanium by fracture of titanium hydride precipitates. CRAIGHEAD et al.1 reported that the hydrogen content normally found in commercial-purity a! titanium (60 to 100 ppm) was sufficient to cause a substantial lowering of the impact strength, and they attributed this embrittling effect of hydrogen to the precipitation of titanium hydride. Lenning et al.&apos; found that in commercial-purity a titanium there is an almost complete loss of impact strength at about 200 pprn H, which is approximately half the value needed to eliminate the impact strength of high-purity a titanium. They also showed that the presence of 3000 ppm hydrogen reduces the room-temperature tensile ductility of commercial-purity material to a value of the order of 10 pct; the corresponding hydrogen concentration for high-purity titanium is over 9000 ppm. It thus appears that the detrimental effect of hydrogen on the mechanical properties of commercial-purity titanium becomes evident at much lower hydrogen contents than for high-purity titanium. The main difference between the two types of a titanium might be expected to be the higher level of interstitial impurity in the commercial-purity grade. Jaffee et a1.3 studied the influence of temperature and strain rate on the hydrogen embrittlement of high-purity and commercial-purity ! titanium. In general, the behavior was the same for both materials; embrittlement was enhanced by decreasing temperature and increasing strain rate. Recent results from tests on commercial-purity a titanium containing 850 ppm O and varying amounts of hydrogen up to -500 ppm showed that the degree of embrittlement by hydrogen is intimately related to the fracture characteristics of titanium hydride precipitates.4 The present paper considers the interrelationship between the mechanical properties and micro-structural features of commercial-purity a! titanium containing 850, 1250, and 2700 ppm 0 and varying amounts of hydrogen up to -500 ppm. 1. EXPERIMENTAL PROCEDURE Three types of commercial-purity titanium supplied by IMI* were used in the investigation, and for the *Address: Witton, Birmingham 6, United Kingdom. purpose of this paper are designated Ti 115, Ti 130, and Ti 160. The principal impurity elements are given in Table I. The material was received in the form of 12.7 mm diam bars having a fully recrystallized structure. Tensile specimens with a round cross-section of 4.5 mm diam and a gage length of 15.2 mm were machined from the bars. In order to develop the same grain size (mean linear intercept of grain boundaries) in each of the three types the specimens were annealed under a dynamic vacuum of <10?5 mm Hg, Table 11. Specimen hydriding was carried out in a modified Sieverts apparatus;&apos; hydrogen was taken into solution at 450°C and after holding the specimens at this temperature for 24 hr they were furnace-cooled to room temperature at an average rate of -100 C deg per hr. By this method nominal hydrogen contents of 0, 50, 100, 250, and 500 ppm were introduced into specimens of Ti 115, Ti 130, and Ti 160 (100 ppm (wt) -0.5 at. pct). The actual hydrogen contents were calculated from the weight differences obtained by weighing the specimens before and after the hydriding treatment. Tensile tests were carried out at temperatures of -196", -78", 20°, 150°, and 300°C on a 10,000 kg In-stron machine at a nominal strain rate of -1.0 x 10-3 sec-1. Fractured specimens were sectioned in planes parallel to the tensile axis, mechanically polished to 0.25 µm grade of diamond paste, and then attack polished using a solution containing by volume 99 parts H2O, 1 part HF, and 1 part HNO3. Although the latter treatment unavoidably opened out cracks and voids visible after mechanical polishing, it did reveal the grain structure, titanium hydride morphology, and deformation twinning structure.

Jan 1, 1970

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins&apos; and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer&apos; type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman&apos;s results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman&apos;s demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman&apos;s experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman&apos;s experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman&apos;s experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman&apos;s Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author&apos;s reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By Pol Duwez

IN the course of an investigation of the V-CO system, two intermediate phases were found. One of these phases corresponds approximately to the stoichiometric composition VCo and is isomorphous with the sigma phase in the Fe-Cr system.&apos; The second phase has the composition V3Co; its crystal structure is described in the present note. The alloys were prepared by mixing the two metals in the powder form, pressing a small disk weighing about 5 g at 80,000 psi, and arc melting this disk on a water-cooled copper plate in an atmosphere of pure helium. The details of this technique have been described.&apos; The vanadium powder was obtained from Westinghouse Electric Corp., Bloomfield, N. J. This powder is probably of very high purity, since when it is properly sintered or melted in the above-mentioned arc furnace, ductile specimens are obtained. The cobalt powder, from Charles Hardy, Inc., New York, contained 0.5 pct Ni, 0.1 pct Cr, and traces of Si and Fe. After melting, the V,Co samples were sealed in evacuated quartz tubes and homogenized for ten days at 800°C. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using Ka copper radiation. The patterns were readily indexed on the basis of a primitive cubic lattice with a parameter equal to 4.675A. The density, determined by the immersion method, was 6.71 g per cu cm; hence the number of molecules per unit cell is approximately 1.95; i.e., 2. At this point, the possibility that the structure might be that of beta tungstena became apparent. The beta tungsten structure is described as follows: Space group 03,, — Pm3n 2 Co in (a) : 000; ?4lhYZ (hhl) reflection present only if 1 = 2n. Assuming this structure to be the correct one, intensities were computed by means of the usual eauation: 1 + cos220 I oc p F sin 0 cos 6 where F is the structure factor, 0 the Bragg angle, and p the multiplicity factor. The observed and calculated values of sin 0 and the intensities are given in Table I. The agreement between the observed and the calculated sin 0 is good and there are no flagrant discrepancies between the calculated intensities and those estimated visually. The (hhl) reflections for which 1 is odd are not observed, as required by the space group. In addition, the (410), (430), and (531) reflections are missing as expected, because of the special (a) and (c) positions in0%. However, six reflections—(llo), (220), (310), (411), (422), and (510)—which have very weak computed intensities were not observed. For these reflections, the structure factor is proportional to the difference between the scattering factors of the two atoms in the structure. Since the scattering factors of vanadium and cobalt are not very different, these reflections are weak. However, by using Ka chromium radiation, whose wavelength is just above the absorption edge of vanadium, the effective scattering factor of vanadium may be decreased by one or two units; consequently the difference between the cobalt and vanadium scattering factors is increased. It was, indeed, found that in a powder pattern taken with chromium Ka radiation, the three reflections (110), (220), and (310) were actually present. The three other reflections (411), (422), and (510), with spacings smaller than half the wavelength of chromium Ka, were obviously not obtainable with chromium radiation. All the experimental results appear to confirm the beta tungsten structure for V,Co. In this structure, each cobalt atom is surrounded by twelve vanadium atoms at 2.61A; each vanadium atom is surrounded by two vanadium atoms at 2.34A, four cobalt atoms at 2.61 A, and eight vanadium atoms at 2.86A. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under contract number W-04-200-ORD-455 with the Army Ordnance Department, Washington, D. C. The author wishes to thank this agency for the permission to publish the results of this investigation. References &apos;P. Duwez and S. R. Baen: X-Ray Study of the Sigma Phase in Various Alloy Systems. Symposium on the Nature, Occurrence, and Effect of Sigma Phase. ASTM Special Tech. Pub. No. 110, pp. 48-54. Philadelphia, 1951. 2 C. H. Schramm, P. Gordon, and A. R. Kaufmann: The Alloy Systems Uranium-Tungsten, Uranium-Tantalum, and Tungsten-Tantalum. Trans. AIME (1950) 188, pp. 195-204; Journal of Metals (January 1950). 3 M. C. Neuburger: The Crystal Structure and Lattice Constants of Alpha and Beta Tungsten. Ztsch. fiir Krist. (1933) 85, pp. 232-237.

Jan 1, 1952

Discussion of the paper of S. E. Bretherton, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1481 to 1487. S. E., BRETHERTON, San Francisco, Cal.:-Since preparing my paper, our chemist, F. L. Wilson, has been experimenting with Leadville, Colo., oxidized zinc ore and Leadville zinc sulphides containing lead, operating upon 40-1b. lots at a time. His results on Leadville sulphides are as follows: The raw ore contained a trace of gold, 5.04 oz. of silver, 19.1 per cent of zinc, and 7.24 per cent of lead. After roasting the ore contained a trace of gold, 5.72 oz. of silver, 0.75 per cent of copper, 21.7 per cent of zinc, and 8.29 per cent of lead. The loss in weight by leaching was 38.8 per cent. The extraction was 42.8 per cent of the copper, 80.6 per cent of the zinc, 7.1 per cent of the lead, 0.64 per cent of the silver, and no gold. The little .silver that is extracted would be thrown down with the copper when precipitating it from the zinc and both thrown hack into the residue to be smelted. There would be no trouble in smelting the residue with nearly all the sulphur eliminated and containing less than 7 per cent. of zinc. On zinc carbonates containing silicates the results are not satisfactory. H. O. HOFMAN, Boston, Mass. (communication to the Secretary*) :¬The paper by Mr. Bretherton upon the application of ammonia and carbonic acid to the recovery of zinc as oxide from roasted sulphide ore is of interest to me, as the first installation of the Schnabel process for the extraction of zinc from a mixture of zinc oxide, lead oxide (with some cupric oxide), and pellets of enriched lead, produced in steaming liquated zinc-silver-lead crust of the Parkes process, was made at Lautenthal, Harz mountains, where I was chemist. In that capacity I carried out numerous experiments on the Schnabel process, was active in the erecting of the plant, and later had charge of it. After the Lautenthal plant had been in operation for some time a similar one was built at Hoboken-les-Anvers, but both have been abandoned, as the wet process could not compete with the distillation of the liquated zinc-silver-lead crust, now used universally in the Parkes process.

Jan 11, 1913